JP2010132524A - Peptide chelate-containing fertilizer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fertilizer which is prepared by reutilizing wastes from the protein industry as a nitrogen source, is inexpensively and easily producible, and exhibits an excellent fertilizing effect. <P>SOLUTION: The fertilizer is composed of hydrolysates of proteins, and a peptide chelate compound formed of a metal ion selected from among iron, zinc, manganese, and copper. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a fertilizer comprising a peptide chelate compound.

  Fertilizers are applied to plants and soil for plant nutrition, or to the land for the purpose of bringing about chemical changes in the soil to contribute to plant cultivation. Essential elements necessary for plant growth are nitrogen, phosphorus, potassium, carbon, oxygen, hydrogen, calcium, magnesium, sulfur, and trace elements such as manganese, iron, copper, zinc, boron, and molybdenum. It is said to be chlorine and is supplied to plants from various fertilizers.

  Fertilizer components are classified into three types: soluble in water, soluble in 2% citric acid, and soluble in 1/2 N hydrochloric acid. Of these, water-soluble fertilizer components are fast-acting and are optimal for urgent applications. To make each element, which is a trace element, a water-soluble fertilizer component, for example, there is a method in which each element is dissolved in water in the form of a sulfate or an oxide salt. There was a problem of insolubilization in the soil. For this reason, a method of chelating each element which is a trace element has been proposed.

  As chelating agents, chain coordination products such as ethylenediamine, bipyridine, EDTA (ethylenediaminetetraacetic acid) and phenatroline, and cyclic coordination substances such as porphyrin and crown ether are used. Recently, amino acids and metals are used. A fertilizer containing a chelate compound formed by mixing with a fertilizer has also been reported (Patent Documents 1 and 2).

  However, since EDTA is expensive, it is economically problematic and there is a problem that EDTA is not decomposed. The amino acid chelate compound is not suitable as a versatile fertilizer because the binding ratio between the amino acid and the metal salt is strict and the amino acid is expensive.

  On the other hand, protein industrial waste, such as cut waste in the leather industry, shaving waste, discarded leather seats for automobiles, fish waste discharged from the fish market, cut meat waste and animals from meat processing plants Wastes such as hair from chickens and chickens, wool waste from clothes garment factories, feathers used for futons, waste from cleaning processes such as down, etc. are emitted from many industries. In particular, leather production by-products, which are said to be incinerated at an annual rate of 22,000 tons as industrial waste, are urgently required to be reused from the viewpoint of environmental protection in CO2 emission regulations.

  On the other hand, as for the chelate of protein hydrolyzate and metal ion, it has been reported that a chelate compound having a molecular weight of 300,000 or less obtained from protein hydrolyzate and ferrous salt can serve as a foam fire extinguisher (Patent Document) 3) It is not known that a protein hydrolyzate forms a chelate in a crude state, and it has not been reported so far as a fertilizer.

JP 2001-151589 A JP 2002-173388 A Japanese Patent Publication No. 3-33031

  The present invention relates to providing a fertilizer that reuses protein industrial waste as a nitrogen source, is inexpensive and can be easily manufactured, and exhibits an excellent fertilizer effect.

As a result of studying the above problems, the present inventors have found that the protein hydrolyzate forms a stable chelate with respect to a metal ion selected from iron, zinc, manganese and copper, and the chelate compound is a fertilizer. It has been found that it functions effectively as an ingredient.
That is, the present invention relates to the following inventions 1) to 8).
1) A fertilizer comprising a protein hydrolyzate and a peptide chelate compound formed from a metal ion selected from iron, zinc, manganese and copper.
2) The fertilizer according to 1) above, wherein the protein hydrolyzate is obtained by treating the protein material with an alkaline solution having a concentration of 5 to 20% (w / v) at 50 to 80 ° C. for 1 to 6 hours.
3) The fertilizer according to 2) above, wherein the protein material is treated with a potassium hydroxide solution (5 to 20% (w / v)) having a bath ratio of 1: 1 to 1: 5.
4) The fertilizer according to any one of 1) to 3) above, wherein the protein hydrolyzate has an average molecular weight of 1,000 to 50,000.
5) The protein material is hydrolyzed at 50 to 80 ° C. for 1 to 6 hours using a potassium hydroxide solution (5 to 20% (w / v)) having a bath ratio of 1: 1 to 1: 5 and neutralized. A peptide chelate compound-containing fertilizer obtained by adding a metal salt selected from iron, zinc, manganese and copper after treatment.
6) The fertilizer according to 2) to 5) above, wherein the protein material is derived from protein waste. 7) The fertilizer according to 6) above, wherein the industrial waste is a leather waste material or a leather manufacturing byproduct.
8) A fertilizer composition containing the fertilizers of 1) to 7) above.

  The peptide chelate compound of the present invention is stable in the soil, is used as a nutrient for plants as a fertilizer, and can be a good agricultural material in the soil environment. Further, since industrial waste such as leather waste and leather production by-products, which are incinerated annually as raw materials, can be used as a raw material, it can be manufactured at low cost, and at the same time, resources can be reused. That is, according to the present invention, a fertilizer with high added value is provided while solving the problems of two aspects of environmental protection and securing of agricultural resources.

The chart which shows the light absorbency change of visible part wavelength range.

In the present invention, examples of the protein hydrolyzate include a product obtained by hydrolyzing a part of a chemical bond existing in a protein using an alkali and reducing the molecular weight of the protein.
Here, the protein material to be used may be either an animal source or a plant source, and is not particularly limited, but it is preferable to use protein waste. Examples of the protein waste include leather waste such as cut waste, shaving waste, leather for seats such as scrap cars, fish waste discharged from the fish market, meat waste from meat processing plants, Examples include wool waste from animals and chickens, wool waste from clothes garment factories, feathers used for futons, feather waste from down, etc., of which leather waste is incinerated in large quantities. It is more preferable to use a product.

  In the hydrolysis treatment, the protein material can be used as it is, but from the viewpoint of reaction efficiency, it is preferable to use an appropriately pulverized one.

  The hydrolysis treatment with alkali is performed by adding the protein material to an aqueous alkali solution. Examples of the alkali include those usually used for hydrolysis of proteins and peptides, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide, ammonia and the like. Although it may be appropriately selected depending on the properties of the target protein raw material, etc., it is preferable to use potassium hydroxide which can be used as it is as a fertilizer component.

Hydrolysis is preferably performed using an alkaline solution having a protein ratio of 1: 1 to 1: 5, more preferably a ratio of 1: 1 to 1: 2 of the protein material.
Here, the bath ratio is the ratio of the mass (g) of the protein material to the liquid volume (ml) of the alkaline solution. That is, the bath ratio is 1: 1 for 100 g of protein material and 100 ml of alkaline solution, and 1: 2 for 100 g of protein material and 200 ml of alkaline solution.
In addition, the alkali concentration may be appropriately selected according to conditions suitable for the target protein raw material, but is preferably in the range of 5 to 20% (w / v), and is preferably 10 to 20% (w / v). More preferred.

  The hydrolysis treatment is performed by shaking or stirring the protein raw material in the above alkaline solution. The reaction is usually preferably carried out within a range of 50 to 80 ° C. for 1 to 6 hours, more preferably at 60 to 70 ° C. for 3 to 6 hours.

  The protein hydrolyzate thus prepared preferably has a mass average molecular weight of 1,000 to 50,000, more preferably 3,000 to 30,000, as measured by exclusion limit chromatography. preferable.

  After completion of the hydrolysis reaction, after neutralizing with an acid such as sulfuric acid, the hydrolyzate may be isolated by filtration, etc., if necessary. In particular, when potassium hydroxide is used as the alkali, it is preferable to perform chelate formation subsequent to hydrolysis and neutralization treatment.

For chelate formation with a metal salt, the metal salt is added at a concentration of 0.1 to 2% by mass, preferably 0.1 to 1% by mass, in an appropriate solvent, with respect to the protein hydrolyzate, and pH 6 to 9, preferably 7 to 9, and can be carried out by stirring at 20 to 40 ° C. for 5 to 30 minutes.
Examples of metal salts include sulfates, nitrates, phosphates, acetates, carbonates, silicates, borates, and chlorides of metals selected from iron, zinc, manganese, and copper. 1 type (s) or 2 or more types can be used.

  The obtained peptide chelate compound can be used as it is as a fertilizer or fertilizer raw material, but depending on the purpose, it can be isolated and used by separation and purification means such as filtration and exclusion limit chromatograph as appropriate. Good.

  The peptide chelate compound thus obtained, as shown in the examples below, is highly stable and applied to the soil, is well absorbed into crops and exerts a fertilizer effect, and its effect is higher than that of an amino acid chelate compound. Are better. Therefore, a solution containing a peptide chelate compound can be used alone as a liquid fertilizer or fertilizer raw material, and can also be pulverized by spray drying or freeze drying, or other organic matter or mineral. It becomes a solid fertilizer or fertilizer raw material that is powdered or molded by blending and adsorbing to, or the like, or blending into powder or solid. In particular, when a protein raw material is hydrolyzed using potassium hydroxide, the treatment solution can be used as it is as a fertilizer or a fertilizer raw material by performing chelate formation subsequent to the neutralization treatment.

In addition to such peptide chelate compounds, known fertilizer components and various carriers such as nitrogenous fertilizer, phosphate fertilizer, calcareous fertilizer, calcareous fertilizer, bitter soil fertilizer, manganese fertilizer, boron fertilizer, such as sugar, An organic acid, a surfactant, a dispersant, a spreading agent and the like can be blended to form a fertilizer composition of any form by a conventional method.
Here, as the nitrogenous fertilizer, for example, nitrate nitrogen-containing fertilizers such as potassium nitrate, sodium nitrate, lime nitrate, and nitric acid, ammonium nitrogen-containing fertilizers such as ammonium sulfate, ammonium nitrate, and sodium ammonium nitrate, and urea nitrogen such as urea A fertilizer containing etc. can be mentioned.
Examples of phosphate fertilizers include, for example, primary ammonium phosphate, secondary ammonium phosphate, primary potassium phosphate, secondary potassium phosphate, superphosphate lime, heavy superphosphate lime, molten phosphorus fertilizer, and corrosion Examples include acid phosphorus fertilizer, calcined phosphorus fertilizer, phosphoric acid bitter soil, and by-product phosphorus fertilizer.
Examples of potash fertilizers include, for example, potassium sulfate, potassium sulfate dough, potassium bicarbonate, corrosive potassium fertilizer, crude potassium salt, coated potassium fertilizer, liquid potassium silicate fertilizer, by-product potassium fertilizer, mixed potassium fertilizer, etc. Can do.
Examples of calcareous fertilizers include quick lime, slaked lime, calcium sulfate, calcium carbonate, calcium nitrate, and calcium phosphate.
Examples of mafic fertilizers include sulfuric acid moulding, hydroxylated moulding, corrosive acid moulding, acetic acid moulding, processed moulding fertilizer, lignin moulding fertilizer, mixed moulding manure, nitric acid moulding, moulding lime, etc. Can be mentioned. Moreover, the molten phosphorus fertilizer etc. which were mentioned as a phosphate fertilizer can be used also as a mafic fertilizer.
As a manganese fertilizer, what has a manganese compound, such as manganese sulfate, as a main component can be mentioned, for example.
Examples of the boron fertilizer include fertilizers containing water-soluble boron such as boric acid fertilizer and borate fertilizer.

The form of the fertilizer composition may be any of liquid, wettable powder, granule, powder and the like.
The content of the peptide chelate compound in the fertilizer composition is preferably 1 to 5% by mass, and more preferably 3 to 5% by mass.

  As a method for supplying the fertilizer or fertilizer composition of the present invention to a plant, various means can be used. For example, spraying the stock solution or diluted aqueous solution directly onto plants such as foliage, stems, fruit trees, or injecting it into the soil, hydroponics, or hydroponic fluid that is in contact with the roots such as rock wool A method of diluting and supplying to water is mentioned.

Example 1 Preparation of Peptide Chelate Compound Using Leather Manufacturing By-product (1) Hydrolysis A leather manufacturing by-product was mixed with a potassium hydroxide solution (concentration 5% to 20% (w / w) in a bath ratio range of 1: 1 to 1:30. v)), the reaction temperature was set to room temperature, 60 ° C and 70 ° C, and hydrolysis was performed for 6 hours.
In addition, what was obtained from Merck Co., Ltd. was used for the leather manufacture by-product.

(2) Concentration 10% (w / v) potassium hydroxide solution, bath ratio 1: 1, 70 ° C. The molecular weight of the hydrolyzate when treated for 6 hours was measured by the following method.
1) Measuring method
Measurement was performed by exclusion limit chromatography using a Shodex PROTEIN KW-802.5 column. Further, MW-MARKER PROTEINS (HPLC) manufactured by Oriental Yeast Co., Ltd. was used as a molecular weight standard product.
2) Results As a result of creating a calibration curve from the elution time of the standard product and calculating the molecular weight of the hydrolyzate, it was confirmed that the molecular weight was 25,000 to 35,000 peptide residues.

(3) Formation of chelate 1) The hydrolyzed solution obtained in (1) (bath ratio 1: 1, potassium hydroxide solution (10% (w / v)), treated at 70 ° C. for 6 hours) is treated with 5 N sulfuric acid. Was used to adjust the pH to 7.5.

2) A chelate compound was prepared by adding a zinc chloride solution (0.2% by mass with Zn) and a ferric ammonium sulfate solution (0.2% by mass with Fe) to the hydrolyzed solution after the neutralization treatment.
As a comparison, a 1N potassium hydroxide solution was added to a zinc chloride solution (0.2% by mass with Zn) and a ferric ammonium sulfate solution (0.2% by mass with Fe), and precipitation of metal hydroxide was observed. As a result of a qualitative test to confirm the presence or absence, precipitation of metal hydroxide occurred when zinc chloride solution and ferric ammonium sulfate solution were added with potassium hydroxide solution. Precipitation was not observed in the metal salt added and reacted. This confirmed that the protein hydrolyzate formed chelate bonds with zinc and iron.
Furthermore, as a result of measuring the absorption spectrum of the visible portion (350 nm to 500 nm) of this peptide chelate solution, a remarkable increase in absorbance was observed when iron was added in the visible portion. This was considered to have caused structural changes within the molecule (FIG. 1).

3) When manganese and copper were subjected to the same test as in 2) under the following conditions, a stable solution could be prepared. Further, as a result of the qualitative test for chelate confirmation described above, the precipitation of metal hydrate did not occur even when a potassium hydroxide solution was added, and peptide chelate formation was confirmed.
a) Hydrolysis: bath ratio 1: 1, potassium hydroxide solution (10% (w / v)), treatment at 70 ° C. for 6 hours b) Chelate formation: manganese sulfate (Mn concentration 0.5 mass%), sulfuric acid Treated with copper (Cu with a concentration of 0.2% by mass) at 25 ° C for 30 minutes

(4) Examination of metal salt concentration The hydrolyzed solution obtained in (1) was neutralized with sulfuric acid. In addition, zinc chloride (0.2 mass%, 0.3 mass%, 0.4 mass%), zinc nitrate (0.2 mass%, 0.3 mass%, 0.4 mass%) as metal zinc element %), Zinc sulfate (0.2 mass%, 0.3 mass%, 0.4 mass%), ferric sulfate as the iron element (0.05 mass%, 0.1 mass%, 0.2 mass%) 0.4 mass%), ferric ammonium sulfate (0.2 mass%, 0.3 mass%, 0.4 mass%), ferric chloride (0.2 mass%, 0.3 mass%, The peptide chelate compound was obtained by stirring and adding at a concentration of 0.4% by weight) and reacting at 25 ° C. for 30 minutes.

  1N potassium hydroxide solution was added to these peptide chelate metals, and the degree of precipitation and the degree of crystal generation at low temperature storage of 4 ° C. were observed. As a result, 0.2% by mass of Fe, Cu, Zn, 0.5% by mass of Mn was the most preferable concentration.

Example 2 Absorption test from soil by irrigation (1) Preparation of test solution 100 g of leather production by-product was mixed with 100 ml of 10% (w / v) potassium hydroxide solution, and the mixture was hydrated by shaking at 70 ° C. for 6 hours. Decomposition was performed.
After the reaction, neutralization treatment was performed using sulfuric acid, and 0.2 mass% of ferric sulfate was added with Fe, and the mixture was stirred at 25 ° C. for 30 minutes to prepare a peptide chelate iron solution.

(2) Preparation of prototype
Komatsuna (Takii) is mixed and filled with 90 mg of nitrogen, 80 mg of phosphoric acid and 80 mg of potassium as fertilizer ingredients in 900 g of black soil (maximum water volume 50 g / 100 g, dry soil) collected from Tochigi Prefecture in a 1 / 10,000 arel size pot. 3-4 seeds were sown in 1 pot and finally thinned to 3 strains per pot. Seven test pots were prepared for each of the test group and the control group. The soil moisture during the preparation period was adjusted to 60% of the maximum water capacity, and Komatsuna was grown.

(3) Test Method The peptide chelate iron solution prepared in (1) was diluted 300 times with water to the prepared Komatsuna pot and 100 cc was irrigated per pot (test group). In the control group, 100 cc of ion-exchanged water was irrigated per pot. The number of irrigation treatments was carried out 7 times every 3 days until the harvest survey. As growth survey items, leaf color, stem length, fresh weight above ground, and iron content in crops were measured.
The iron content was measured by atomic absorption photometry.
The leaf color was measured using a chlorophyll meter SPAD-502 manufactured by Konica Minolta Sensing Co., Ltd.
(4) Test results From Table 1, the growth of Komatsuna was promoted by the irrigation treatment of peptide chelate iron (test group), and the leaf length and fresh weight were also higher than the control group, showing vigorous growth.
Moreover, as shown in Table 2, it was confirmed that the iron content in the Komatsuna body increased and the peptide chelated iron was absorbed by the crop.
From the above, it was confirmed that the peptide chelate compound of the present invention has an excellent fertilizer effect.

Example 3 Comparison test between peptide chelate iron and amino acid chelate iron (1) Preparation of test solution A peptide chelate iron solution was prepared in the same manner as in Example 2 (1), and alanine chelate iron solution as amino acid chelate iron to be compared Was prepared for testing.
As the alanine chelate iron solution, an alanine solution having nitrogen equivalent to the total nitrogen content in the solution of Example 2 was prepared, and 0.2% by weight of ferric chloride was added to Fe at 30% at 25 ° C. Prepared by stirring for minutes.

(2) Preparation of a prototype The seeds of Komatsuna were sown on rock wool, and after germination, seedlings were grown in a hydroponic culture solution not containing iron, and Komatsuna seedlings in an iron-deficient state were produced in 4 pots in each test area, 20 strains .

(3) Test method The leaves prepared by diluting the solution prepared in (1) 100 times each to the iron-deficient Komatsuna seedlings prepared in (2) were sprayed. As a control, ion-exchanged water was sprayed. From the initial spraying, foliar spraying was performed once a day for a total of 5 times to measure the fresh weight of Komatsuna and the green strength of the leaves.

(4) Test results As shown in Table 3, there was no change in the fresh weight per pot, but the green strength of the leaves at the end of the test (SPAD-502, manufactured by Konica Minolta) As a result of measurement, the SPAD value decreases in the order of peptide chelate iron> alanine chelate iron> ion exchanged water, and it is confirmed that the leaf color becomes lighter according to the decrease of SPAD value even by visual judgment. It was.
Iron is essential for increasing the leaf color of plants and increasing the amount of chlorophyll required for photosynthesis. From the above, it has been found that the absorption is more effective in the structure in which a chelate bond is formed with the peptide than the amino acid chelate iron, and the peptide chelate compound of the present invention including peptide chelate iron has an excellent fertilizer effect. It has been confirmed that it works.

Claims (8)

  A fertilizer comprising a protein hydrolyzate and a peptide chelate compound formed from a metal ion selected from iron, zinc, manganese and copper.   The fertilizer according to claim 1, wherein the protein hydrolyzate is obtained by treating a protein material with an alkaline solution having a concentration of 5 to 20% (w / v) at 50 to 80 ° C for 1 to 6 hours.   The fertilizer according to claim 2, wherein the protein material is treated with a potassium hydroxide solution (5 to 20% (w / v)) having a bath ratio of 1: 1 to 1: 5.   The fertilizer according to any one of claims 1 to 3, wherein the protein hydrolyzate has a mass average molecular weight of 1,000 to 50,000.   The protein material was hydrolyzed at 50 to 80 ° C. for 1 to 6 hours using a potassium hydroxide solution (5 to 20% (w / v)) having a bath ratio of 1: 1 to 1: 5, and neutralized. A peptide chelate compound-containing fertilizer obtained by adding a metal salt selected from iron, zinc, manganese and copper.   The fertilizer according to any one of claims 2 to 5, wherein the protein material is derived from protein waste.   The fertilizer according to claim 6, wherein the industrial waste is a leather waste material or a leather manufacturing by-product.   The fertilizer composition containing the fertilizer of any one of Claims 1-7.

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